Systems and methods for x-ray emission spectroscopy are provided in which at least one x-ray analyzer is curved and receives and diffracts fluorescence x-rays emitted from a sample, and at least one spatially-resolving x-ray detector receives the diffracted x-rays. The at least one x-ray analyzer and the at least one spatially-resolving x-ray detector are positioned on the Rowland circle. In some configurations, the fluorescence x-rays are emitted from the same surface of the sample that is irradiated by the x-rays from an x-ray source and the system has an off-Rowland circle geometry. In some other configurations, an x-ray optical train receives the fluorescence x-rays emitted from a sample impinged by electrons within an electron microscope and focuses at least some of the received fluorescence x-rays to a focal spot.